KR0147307B1 - Photosensitive resin composition and semiconductor device using it - Google Patents

Abstract

The present invention is an essential component, (A) a polyamic acid having a repeating unit represented by the following formula (I),

In the above formula, 0.5 to 50 mol% of R ₁ is composed of a silicone diamine residue represented by the following formula (II),

(Wherein N represents an integer of 1 to 50) The remaining 50 to 99.5 mol% of R ₁ is composed of an organic group selected from the group consisting of an aromatic group, an aliphatic group, an aliphatic ring group and a heterocyclic group, and R ₂ is an aromatic group , An aliphatic group, an aliphatic ring group, a heterocyclic group and an organic group selected from the group consisting of a silicone group, m is 1 or 2.

(B) an amide compound having a carbon-carbon double bond, and

(C) The photosensitive resin composition containing a photosensitizer is provided.

The present invention also provides a semiconductor device in which the above composition is used.

Description

Photosensitive resin composition and semiconductor device using the same

The present invention relates to a high sensitivity and high resolution photosensitive resin composition capable of providing a polyamide film useful for a semiconductor device, and also to a semiconductor device made using the composition.

Until now, polyamide resins having better heat resistance and excellent electrical and mechanical properties have been used for interlayer dielectrics of surface protection films and semiconductor parts. In recent years, many improvements in thermal cycle resistance and thermal shock resistance have been required for the expansion and integration of semiconductor components, thinning and shrinking of sealing resin packages, and moving to surface mounting methods by solder reflowing. And conventional polyamide resins could hardly satisfy this requirement.

For this purpose, it has been proposed to introduce a silicone component into a polyamide resin to improve adhesion and reduce elastic modulus (Japanese Patent Laid-Open Nos. 61-64730 and 62-223228).

On the other hand, a recent interest is the technique of giving photosensitivity to the polyamide resin itself.

The use of these polyamide resins provided with photosensitivity simplifies the pattern forming step compared to those with non-photosensitive polyamide resins, and also eliminates the need for highly toxic etching solutions, thus preventing environmental pollution and ensuring safety. desirable.

Therefore, the photosensitization of the polyamide resin is expected to be an important technique along with the improvement of the adhesion and the decrease of the elastic modulus of the polyamide resin.

As the photosensitive polyamide resin, a composition containing a polyamide precursor having a photosensitive property as an ester group and having a structure represented by the following formula (X) (e.g., Japanese Patent Publication No. 55-41422):

And a polyamic acid having a structure represented by the following formula (Y) added to a compound containing a carbon-carbon double bond and an amino group or a quaternary salt thereof which is dimerizable or polymerizable by actinic radiation (e.g., Japan National Patent Publication No. 59-52822):

This is known.

After dissolving these compositions in a suitable organic solvent, coating and drying in a varnish state, the coated film is irradiated with ultraviolet light through a photomask, then developed and rinsed to obtain a desired pattern, and further Heat treatment to form a polyamide film.

However, conventional compositions have the following drawbacks. That is, the composition containing the polyamide precursor represented by (X) is produced through a very complicated step of first esterifying an alcohol having a photosensitive group with tetracarboxylic dianhydride and then amidating the esterified product with diamine. , It is difficult to stabilize the product. However, since the ester bond has a strong binding force, this composition has the advantage of being able to use spray development (rapid short time development by violent spraying of the developing solution). On the other hand, since the bonding force is too strong, the photosensitive group cannot be completely removed even at a temperature higher than 400 ° C., resulting in blackening the resulting polyamide film and degrading the properties (strength, elongation, etc.) of the film. The composition containing the polyamic acid represented by (Y) can be prepared only by mixing the polyamic acid and the photosensitizer, so the manufacturing step is very simple, but the ionic binding force between the polyamic acid and the photosensitizer is very weak, so that the paddle phenomenon Development by dropping the developing solution), and processing latitude during development is narrow. Moreover, the viscosity change of the varnish at room temperature is large and lacks storage stability, which is insufficient for semiconductor manufacturing applications. On the other hand, since the composition has a weak bonding force, the photosensitizer can be easily removed by heat and has the advantage of excellent properties of the resulting polyamide film. However, the exposure sensitivity of the two compositions containing (X) and (Y) is 500-1000 mJ / cm 2, which is not sufficient to satisfy the requirement for improvement of sensitivity according to recent technological advances.

When such conventional photosensitization techniques are used for polyamide resins having high adhesion, low modulus and incorporation of silicon groups, patterning by irradiation of ultraviolet rays is difficult or very low in sensitivity, and thus is generally used in the semiconductor industry. It is difficult to process polyamide resin by the apparatus.

The object of the present invention is as follows:

(1) providing a photosensitive resin composition having a significantly high sensitivity and resolution,

(2) providing a photosensitive resin composition having no change in quality by a simple method,

(3) It is to provide a photosensitive resin composition which is excellent in the properties of the film after reinforcement and can easily obtain a highly reliable polyamide film when used in a semiconductor device, or to provide a semiconductor device made using such a composition.

The present invention is a photosensitive resin composition containing the following components as essential components:

(A) a polyamic acid having a repeating unit represented by the following formula (I),

In the above formula, 0.5 to 50 mol% of R ₁ is composed of a silicone diamine residue represented by the following formula (II),

(Wherein n represents an integer of 1 to 50)

The remaining 50 to 99.5 mol% of R ₁ is composed of an organic group selected from the group consisting of an aromatic group, an aliphatic group, an aliphatic ring group and a heterocyclic group, and R ₂ is an aromatic group, an aliphatic group, an aliphatic ring group, a heterocyclic group and a silicon group Consisting of organic groups selected from the group consisting of m is 1 or 2.

(B) an amide compound having a carbon-carbon double bond, and

(C) photosensitizers.

The ratio of the polyamide (A), the amide compound (B) and the photosensitizer (C) is 10 to 500 parts by weight, preferably 50 to 200 parts by weight of the amide compound (B) per 100 parts by weight of the polyamic acid (A). And a photosensitizer (C) is 0.1-50 weight part, Preferably it is 1-10 weight part.

When an amide compound (B) which is liquid at room temperature is used as a photosensitive agent and a solvent to be described below, the amount of the amide compound (B) is a compound which is substantially present as a photosensitive agent after the amount of the compound (B) corresponding to the solvent has evaporated ( B) amount.

Silicone diamines corresponding to formula (4) used in the present invention have the effect of increasing the adhesion or reducing the elastic modulus and increasing the adhesion of the resulting polyamide film.

The degree of polymerization n of the silicone diamine should be from 1 to 50.

If it is less than 1, the effect of increasing adhesion and decreasing elastic modulus cannot be obtained, and if it is larger than 50, i.e., using a long chain silicone diamine, the reaction with tetracarboxylic dianhydride can hardly proceed quantitatively. The diamine remains as an unreacted substance, which results in not only an increase in molecular weight, but also a decrease in flexibility and a tendency to crack.

The amount of silicone diamine should be 0.5 to 50 mol% relative to the total amount of diamine. If it is less than 0.5 mol%, the effect of increasing adhesion and reducing elastic modulus cannot be obtained, and if it is larger than 50 mol%, heat resistance is greatly reduced and inherent properties as a polyamide resin cannot be obtained.

As the diamine component corresponding to H ₂ NR ₁ -NH ₂ , the following aromatic diamines, aliphatic diamines, aliphatic diamines or heterocyclic diamines are used together with the above silicone diamines imparting various properties: for example m-phenyl Rendiamine, 1-isopropyl-2, 4-phenylenediamine, p-phenylenediamine, 4, 4'- diminophenylpropane, 3, 3'- diminodiphenylpropane, 4, 4'-diamino Diphenylethane, 3, 3'-diaminodiphenylethane, 4, 4'-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 4, 4'-diaminodiphenylsulfide, 3 , 3'-diaminodiphenylsulfide, 4, 4'-diaminodiphenylsulfone, 3, 3'-diaminodiphenylsulfone, 4, 4'-diaminodiphenylether, 3, 3'-dia Minodiphenylether, benzidine, 3, 3'-diaminobiphenyl, 3, 3'-dimethyl, 4, 4'-diaminobiphenyl, 3, 3'-dimethoxybenzidine, 4, 4-diamino- p-terphenyl, 3, 3-diamino-p-terpe , Bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl- 4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, 4-bis (β-amino- t-butyl) toluene, 2, 4-diaminotoluene, m-xylene-2, 5-diamine, p-xylene-2, 5-diamine, m-xylenediamine, p-xylenediamine, 2, 6-diamino Pyridine, 2, 5-diaminopyridine, 2, 5-diamino-1, 3, 4-oxadiazole, 1,4-diamonocyclohexane, piperazine, methylenediamine, ethylenediamine, propylenediamine, 2, 2-dimethylpropylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2, 5- dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, heptamethylenediamine, 2, 5-dimethylheptamethylenediamine, 3- Methylheptamethylenediamine, 4, 4-dimethylhepta Tylenediamine, octamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, 2, 5-dimethylnonamethylenediamine, decamethylenediamine, 1, 10-diamino-1, 10-dimethyldecane, 2, 11-dia Minododecane, 1, 12-diaminooctadecane, 2, 12-diaminooctadecane, 2, 17-diaminoeicoic acid, 2, 6-diamino-4-carboxybenzene, and 3, 3'- Diamino-4, 4'-dicarboxybenzidine, the present invention is not limited to their use.

Preferably used for the preparation of polyamic acids The corresponding aromatic or aliphatic ring or heterocyclic tetracarboxylic dianhydride may be used alone or in combination of two or more thereof. Aromatic or aliphatic or heterocyclic tetracarboxylic dianhydrides are as follows: pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4' -Benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'- Benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, naphthalene- 2,3,6,7-tetra carboxylic dianhydride, naphthalene-1,2,5,6-tetra carboxylic dianhydride, naphthalene-1,2,4,5-tetra carboxylic dianhydride, naphthalene -1,4,5,8-tetra carboxylic dianhydride, naphthalene-1,2,6,7-tetra carboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7 Hexahydronaphthalene-1,2,5,6-tetra carboxylic dianhydride, 4,8-dimethyl-1,2,3,4,5,6,7-hexahydronaphthalene-2,3,6, 7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetra carboxylic dianhydride, 2,7-dichlorona Phthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetra carboxylic acid dianhydride, 1,4,5 , 8-tetrachloronaphthalene, 2,3,6,7-tetra carboxylic dianhydride, 3,3 ', 4,4'-diphenyltetra carboxylic dianhydride, 2,2', 3,3 ' -Diphenyltetra carboxylic dianhydride, 2,3,3'4'-diphenyltetra carboxylic dianhydride, 3,3,4,4-p-terphenyltetra carboxylic dianhydride, 2,2 , 3,3-p-terphenyltetracarboxylic dianhydride, 2,3,3,4-p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydrides, 2,2-bis (2,3-dicarboxyphenyl) ether dianhydrides, bis (3,4-dicarboxyphenyl) ether dianhydrides, bis (2,3-dicarboxyphenyl) ether dianhydrides, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1 , 1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetra carboxylic acid Dianhydrides, perylene-3,4,9,10-tetra carboxylic acid dianhydrides, perylene-4,5,10,11-tetra carboxylic acid dianhydrides, perylene-5,6,11,12- Tetra carboxylic dianhydride, phenanthrene-1,2,7,8-tetra carboxylic dianhydride, phenanthrene-1,2,6,7-tetra carboxylic dianhydride, phenanthrene-1,2, 9,10-tetra carboxylic dianhydride, cyclopentane-1,2,3,4-tetra carboxylic dianhydride, pyrazine-2,3,4,5,6-tetra carboxylic dianhydride pyrrolidine -2,3,4,5-tetracarboxylic dianhydride and thiophene-2,3,4,5-tetra carboxylic acid dianhydride. The invention is not limited to their use.

In addition to the aromatic or aliphatic or heterocyclic tetracarboxylic dianhydrides described above, silicone tetracarboxylic dianhydrides or aliphatic tetracarboxylic dianhydrides may be used together with the dianhydrides to impart various characteristics. to be.

Available for the preparation of polyamic acids Trimellitic anhydride and the like can be used as the aromatic tricarboxylic anhydride corresponding thereto.

The polyamic acid used in the present invention can generally be obtained by reacting tetracarboxylic dianhydride with diamine in a reaction solvent as shown below. Reaction solvents are known organic polar solvents having functional groups and dipole moments which do not react with acid anhydrides and diamines.

The organic polar solvent should be inert to the reactor, solvent to the product and solvent to at least one, preferably two reaction components.

Typical examples of the solvent include N, H-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl Sulfoxide, hexamethylphosphamide, N-methyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, methylformamide, N-acetyl-2-pyrrolidone, diethylene glycol Monomethyl ether and diethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more thereof. Poor solvents such as benzene, benzonitrile, dioxane, butyrolactone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, xylene, toluene and cyclohexane can be used in combination with the above solvents.

The degree of polymerization of the polyamic acid (A) of the present invention is preferably 10 to 10,000, more preferably 20 to 500. If the degree of polymerization is less than 10, the mechanical strength and heat resistance of the resulting cured film are lowered. If the degree of polymerization is higher than 10000, the viscosity of the resin is increased, coating operation is difficult, development takes a long time and productivity is reduced.

If polyamic acid (A) having the actinic reactor P ^* introduced at both ends is used, the exposure sensitivity can be increased and this is useful. P ^* having an acryl group or a methacrylic group used in the acid anhydride-terminated polyamic acid (A) represented by the following formula (III) is generally selected from alcohols having an acryl group or a methacrylic group.

[Wherein m 'is an integer of 10 to 10000, R ₁ and R ₂ are as defined in formula (III) above, and P ^* is

(Wherein n 'is 1 to 5, R ₃ represents H or CH ₃ and R ₄ represents an organic residue).] As an alcohol compound having an acryl group or a methacryl group, for example, 2-hydroxy Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol acrylate methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropylacrylate, 4 Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol modified acrylate, polypropylene glycol modified acrylate, polyethylene glycol modified meta Acrylate, polypropylene glycol modified methacrylate, pentaerythritol triacrylate, pentaerythritol torimethacryl , Pentaerythritol acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, 1,3-diacryloylethyl-5 -Hydroxyethyl isocyanurate, 1,3-dimethacryloylethyl-5-hydroxyethyl isocyanurate, ethylene glycol modified pentaerythritol triacrylate, propylene glycol modified pentaerythritol triacrylate , Trimethylolpropane diacrylate and trimethylolpropane dimethacrylate. The present invention is not limited to the use of these alcohol compounds. These can be used individually or in mixture of 2 or more.

An example of a process for preparing the acid anhydride-terminated polyamic acid represented by formula (III) is as follows: If a degree of polymerization m 'of polyamic acid is 1000, first 1001 moles of acid anhydride n moles of silicone diamine (generally 1 n500 and the appropriate amount depends on the molecular weight of the silicone diamine used) and 2 moles of an alcohol compound having P ^* having an acryl or methacryl group, and then the reaction product is reacted with (1000-n) moles of diamine. Polyamic acid is obtained.

Since the polyamic acid (III) has P * having acrylic or methacrylic groups at both ends, the crosslink density of the exposed portion of the resulting coating film increases, while the unexposed portion is highly soluble and does not crosslink. Since there is no reactor P *, the difference in solubility between the exposed and unexposed portions can be increased and thus the sensitivity can be improved. Furthermore, since both ends of the polyamic acid are protected by actinic reactor P *, depolymerization of the polyamic acid is not seen, so that a resin having excellent viscosity stability can be obtained.

Examples of the amide compound (B) having a carbon-carbon double bond are as follows: acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylamide, N-diethylacryl Amide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dibutylacrylamide, N-acryloylpiperidine, N-acryloylmorpholine, N, N-dimethylmetha Krillamide, N, N-diethyl methacrylamide, N, N-dimethylaminoethyl methacrylamide, N, N-dimethylaminopropyl methacrylamide, N-methylol acrylamide, N-methanol methacrylamide, N -Methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, N-isopropoxymethylacrylamide, N-isopropoxymethylmethacryl Amide, Nn-butyloxymethylacrylamide, Nn-butyoxyoxymethylmethacrylamide, Nt-butik Methylacrylamide, Nt-butyloxymethylmethacrylamide, N, N-dimethylolacrylamide, N, N-dimethylolmethacrylamide, dimethylene ether diacrylamide, dimethylene ether dimethacrylamide, methylenebis Ether type condensates of acrylamide, methylenebismethacrylamide, diacetoneacrylamide, diacetonemethacrylamide, N-vinylpyrrolidone and N-methylolacrylamide or N-methylolmethacrylamide with polyhydric alcohols There is this. These amides may be used alone or in combination of two or more.

For example, Japanese Patent Laid-Open No. 62-273260 is known to add an amide compound having a carbon-carbon double bond of the present invention as an additive to an already photosensitive resin composition.

However, a photosensitive polyamic acid resin composition containing the amide compound itself as a component for imparting photosensitivity is not known.

Conventional techniques consist mainly of adding or introducing acrylic or methacrylic acid esters to polyamic acids, and the present inventors have a new interest in amide compounds having carbon-carbon double bonds.

Since the amide compound having a carbon-carbon double bond is excellent in solubility in polyamic acid, the photosensitizer can be uniformly incorporated in high concentration or has high photoreactivity. Therefore, the photosensitive resin composition which can provide the pattern of high sensitivity and high resolution can be obtained easily. In addition, since the photosensitive group is not introduced into the polyamic acid through direct covalent bond in the present invention, the resulting cured film has excellent properties and excellent effect that the amide compound having a carbon-carbon double bond is easily dispersed as heat during thermal curing. Obtains the effect simultaneously.

In the case of using acrylic esters in conventional techniques, the mixture form described in Japanese Patent Publication No. 59-52822 requires 30 minutes of heating even at 350 ° C., and Japanese Patent Publication Nos. 55-30207 and 41422 The reaction form described in requires heating for 1 hour at 400 ° C. for curing. Thus, the final cured product became quite black and in the worst case crumbled and a strong film could not be obtained.

In the present invention, the use of amide compounds having carbon-carbon double bonds that are liquid at room temperature is more useful. Such amide compounds are generally liquid at 10 to 30 ° C., for example, N-methyl acrylamide, N-ethyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N, N-dimethylacrylic Amide, N, N-diethylacrylamide, N, N-dibutylacrylamide, N-acryloylpiperidine, N-diethyl methacrylamide, N, N-diethyl methacrylamide, N- (2 -Dimethylaminoethyl) methacrylamide, N- (3-dimethylaminopropyl) methacrylamide and N-vinylpyrrolidine. The present invention is not limited to the use of these amide compounds.

These amide compounds, which are liquid at room temperature, generally exhibit good solubility in diamines and tetracarboxylic dianhydrides and polyamic acids, which are starting materials of polyamic acids. Therefore, these amide compounds which are liquid at room temperature can be used for the preparation of polyamic acid instead of the usual solvents.

Conventional reaction solvents are reactive toward light, and therefore, a photosensitive component is added specially in preparing the photosensitive resin. In this case, however, the photosensitive component is diluted with a large amount of the reaction solvent, so there is a limit to increasing the concentration of the photosensitive component.

On the other hand, according to the present invention in which the above-mentioned amide compound is used as the solvent, since the solvent itself is completely photosensitive, the concentration of the photosensitive component is very high and the photosensitivity can be significantly improved. Moreover, since the manufacturing method of the photosensitive resin composition which concerns on this invention consists only of adding and mixing a reactive component, the method is very simple and the change of quality is very few.

N-methylol (or N-alkoxymethyl) acryl (or methacryl) amide used in the present invention is a highly reactive N-methylol or N-alkoxymethyl group and a photosensitive acrylamide or methacryl in one molecule. It is a compound having an amide group. That is, in N-methylol (or N-alkoxymethyl) acrylic (or methacryl) amides, the N-methylol or N-alkoxy methyl groups are first subjected to a thermal drying step to vaporize the solvent upon formation of the light-pattern. It leads to a heat-condensation reaction, and also acrylamide or methacrylamide groups cause a light-crosslinking reaction in the light irradiation step, so that a highly sensitive light-pattern can be formed.

N-methylol (or N-alkoxymethyl) acryl (or methacryl) amides are generally obtained by reacting acryl or methacrylamide with formalin and alcohols.

Among the above-mentioned amide compounds having carbon-carbon double bonds, N-methylol (or N-alkoxymethyl) acryl (or methacryl) amides include the following: N-methylolacrylamide, methylol Methacrylamide, N-methoxymethylacrylamide, N-methoxymethacrylamide, N-ethoxymethylacrylamide, N-ethoxymethacrylamide, N-isopropoxymethylacrylamide, N-isopropoxy Methyl methacrylamide, Nn-butyloxymethylacrylamide, Nn-butyloxymethylmethacrylamide, Nt-butyloxymethylacrylamide, Nt-butyloxymethylmethacrylamide, N, N-dimethylolacrylamide and N, N-dimethylol methacrylamide, The present invention is not limited to the use of these amide compounds.

In addition, when the N-methylol (or N-alkoxymethyl) acrylic (or methacryl) amide is thermally reacted in a weak acid having an acidity such as polyamic acid, a dimerization reaction occurs with dehydration to cause dimethylene ether diacryl. Amide or dimethylene ether dimethacrylamide is obtained. They are also excellent in solubility with respect to polyamic acid, and the use of these produces a highly sensitive photosensitive resin composition.

In this invention, the condensate of another form of an amide compound and an alcohol can be used as an amide compound.

Ether type condensates of N-methylol acrylamide or N-methylol methacrylamide with polyhydric alcohols are compounds having two or more photo-reactive acrylamide or methacrylamide groups in one molecule. Ether-type condensates of N-methylolacrylamide or N-methylolmethacrylamide with polyhydric alcohols are not only highly soluble in polyamic acids but also acrylamide or methacrylamide groups in the light irradiation step of photo-pattern formation. As a result of the photo-crosslinking reaction, the photo-pattern of high sensitivity and high resolution can be formed.

Ether type condensates of N-methylolacrylamide or N-methylolmethacrylamide with polyhydric alcohols can generally be obtained by reaction using an acid such as phosphoric acid as a catalyst.

As the polyhydric alcohol, for example, ethylene glycol, dimethylene glycol, tetraethylene glycol, polyethylene glycol, 1,4-butanediol, 1,3-butanediol, glycerin, pentaerythritol, polyvinyl alcohol, triethanolamine, N-methyldi Ethanolamine, diethanolamine and N-phenyldiethanolamine. The present invention is not limited to the use of these polyhydric alcohols. In addition to these acrylamides, acrylic acid esters can also be added to impart various properties.

Dialkylamino acrylates or methacrylates are excellent in solubility in polyamic acids in acrylic esters and can increase the sensitivity of the composition. Examples of dialkylamino acrylates or methacrylates include N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-di Ethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylate and N, N-dimethylaminopropyl acrylate. The invention is not limited to their use.

The addition amount of amino acrylate is 1-100 weight part with respect to 100 weight part of polyamic acid, Preferably it is 5-30 weight part.

The photosensitizer (C) used in the present invention is irradiated with light to effectively generate radicals or ions and accelerate the photo-reaction of amide compounds having carbon-carbon double bonds.

As a photosensitizer used for this invention, for example, benzophenone, acetophenone, anthrone, p, p'- tetramethylamino benzophenone (Micler's ketone), phenanthrene, 2-nitrofluorene, 5 -Nitroacenaprene, benzoquinone, N-acetyl-p-nitroaniline, p-nitroaniline, 2-ethylanthraquinone, 2-t-butylanthraquinone, N-acetyl-4-nitro-1-naphthylamine , Picramid, 1,2-benzoanthraquinone, 3-methyl-1,3-diaza-1,9-benzoanthrone, p, p'-tetraethyldiaminobenzophenone, 2-chloro-4- Nitroaniline, dibenzylacetone, 1,2-naphthoquinone, 2,5-bis (4'-diethylaminobenzyl) cyclopentane, 2,6- (bis 4'-diethylaminobenzyl) cyclohexa, 2,6- (bis 4'- dimethylaminobenzal) -4-methylcyclohexa is 2,6- (bis 4'-diethylaminobenzal) -4-methylcyclohexa is 4,4'-bis ( 1,3-bis (4) which is dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, and p-dimethylaminobenzylidene '-Dimethylaminobenzyl) acetone, 1,3-bis (4'-diethylaminobenzyl) acetone, N-phenyldiethanol amine, Np-tolyldiethylamine, styryl compound and coumarin compound and also 2,2 Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylrio) phenyl] -2-morpholino-1-propane, 3,3 ', 4, 4'-tetra (t-butylperoxy carbonyl) benzophenone, benzyl, benzoin-isopropyl ether, benzoin-isobutyl ether, 4,4'-dimethoxybenzyl, 1,4-dibenzoylbenzene, 4 -Benzoylbiphenyl, 2-benzoylnaphthalene, methyl-o-benzoylbenzoate, 2, 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-ratio Imidazole, 10-butyl-2-chloroacridone, ethyl-4-dimethylaminobenzoate, dibenzoylmethane, 2,4-diethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-silver, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-silver , 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1- is 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1- Phenylpropanebutanedione-2- (o-benzoyl) oxime, 1,2-diphenylethanedione-1- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (o-benzoyl) oxime , 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, glycine compound and oxazolone compound.

The invention is not limited to the use of these compounds as illustrated. These can be used individually or in mixture of 2 or more types.

In addition, the photosensitizer used in the present invention is preferably a compound having an absorption maximum wavelength (λ max) of 300 to 500 nm. If λ max is less than 300 nm, light is absorbed by the polyamic acid itself, and no photo-reaction occurs. On the other hand, if it is larger than 500 nm, the photo-reaction takes place in visible light, so the work room must be a blocking room and thus the handling is low. Examples of such photosensitizers are as shown below. This invention is not limited to these, These photosensitizers can be used individually or in mixture of 2 or more types.

When the styryl compound represented by the following formula (XI) is used as the photosensitizer component, the sensitivity is improved, and therefore it is preferable to use it.

Wherein R ₁₂ : -H, -CH ₃ , -C ₂ H ₅ or -C ₆ H ₅ , R ₁₃ :

or

(R; H, CH ₃ , C ₂ H ₅ )

Moreover, when a glycine compound represented by a following formula (XII) is used as a photosensitizer component, a sensitivity will further improve. It is particularly preferable to use such glycine compounds together with the above-mentioned absorption compounds having a maximum wavelength of 330 to 500 nm or the above-mentioned styryl compounds.

_{Wherein, R 14: -H, -CH 3} , -C 2 H 5, -C 6 H 5, -OCH 3, -OCOCH 3, -OC 2 H 5, -OCOC 2 H 5, -N (CH 3 ) ₂ , -N (C ₂ H ₅ ) ₂ , -NHCOOCH ₃ , -COCH ₃ , -COC ₂ H ₅ , -NHCONH ₂ , -CH ₂ OH, -OH, -CH (CH ₃ ) ₂ , or -C (CH ₃ ) ₃ ,

In addition, as a photosensitizer component, it is preferable to use the biscumarin compound substituted with the carbonyl group in the 3-position shown by following formula (46).

(Wherein R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkoxy group or a dialkylamino group)

It is particularly preferable to use these biscumarin compounds together with the glycine compounds mentioned above. Moreover, it is preferable to use the oxazolone compound shown by following formula (47) as a photosensitizer (C).

(In the above formula,

R ₁₈ : -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₆ H ₅ , -OH, -OCH ₃ , or -OC ₂ H ₅ .

In particular, it is preferable to use such an oxazolone compound together with a compound having a maximum absorption wavelength of 330 to 500 nm mentioned above, a styryl compound mentioned above or a biscumarin compound mentioned above.

An adhesive aid, a leveling agent, and other additives can be added to the photosensitive resin composition of the present invention.

The photosensitive resin composition of this invention can be used, for example by the following method. In other words, the composition is coated on a suitable support such as silicon wafer, ceramic organ or aluminum organ. Coating is carried out by chipin coating with spinner, spray coating with spray coater, dip coating, printing, roll coating and the like. Thereafter, the coated film is dried under pre-baking at a temperature of 60 to 80 ° C. Thereafter, actinic rays are irradiated onto the film in the form of a desired pattern. X-rays, electron beams, ultraviolet rays, visible rays and the like are used as actinic rays, but the wavelength is preferably 200 to 500 nm.

Subsequently, the relief pattern was dissolved by dissolving the unirradiated portion with a developing solution.

To obtain. As the developing solution, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, methanol, isopropyl alcohol, water and the like are used alone or in combination thereof. The development is carried out by spraying, paddle, dip or ultrasonic development.

Next, the relief pattern formed by development is rinsed. As the rinse solution, methanol, ethanol, isopropyl alcohol, butyl acetate and the like can be used. The relief pattern is then heat treated to form an amide ring and to yield a final pattern with high heat resistance.

The photosensitive resin composition of the present invention can be mainly used in electronic materials such as semiconductor devices as shown below mainly in the form of composites with inorganic materials.

(i) The semiconductor device which coats a composition on the surface of a semiconductor component like IC or LSI, exposes, develops, and hardens to form a pattern and uses it as a surface stabilizing film, a buffer film, or an alpha ray protective film.

(ii) coating a composition on a semiconductor component such as an IC or LSI, exposing, developing and curing to form a pattern, also wiring conductor circuits, connecting to the conductor underlayer and repeating this to insulate the resin between the multilayer wirings. A semiconductor device to be used as a film.

(iii) A semiconductor device in which a pattern is formed on a substrate such as silicon, alumina, etc., an insulating layer is finished, a conductor circuit is wired, and the circuit is repeatedly connected to a semiconductor component.

The photosensitive resin composition of this invention is useful not only for a semiconductor but also for the insulation film layer of a multilayer circuit, the cover coat of a flexible copper-coated sheet, a soldering resist film, the liquid crystal derived from a film, etc.

In order to improve adhesion and decrease elastic modulus, an introduction of siloxane bonds into the main chain of polyamide resin was attempted. However, according to the conventional photosensitization technique, the photosensitivity of the silicone-modified polyamide resin can be improved and an excellent pattern cannot be formed. On the other hand, according to the present invention, the photosensitive resin composition can be obtained by a very simple operation of adding an amide compound (B) having a carbon-carbon double bond and a photosensitizer (C) to the silicone-modified polyamic acid (A). have. Therefore, not only the manufacturing cost is low but also the compound having a carbon-carbon double bond is easily mixed with the polyamic acid by the amide group, so that the photosensitizer can be incorporated into the polyamic acid with high concentration uniformly.

In addition, by adding the photosensitizer component, it is possible to easily obtain a photosensitive resin composition capable of providing a pattern of high sensitivity and high resolution.

Moreover, such a photosensitive resin composition is easily obtained by adding a photosensitive agent, and since the photosensitive group is not introduced into the polyamic acid through direct covalent bond, the photosensitive agent can be easily dispersed by heat at the time of curing, and the performance of silicone, modified polyamide The excellent effect of high adhesion and low modulus of elasticity can be obtained simultaneously. Therefore, the semiconductor device can be easily processed into the present composition to obtain a highly reliable semiconductor device.

There is also no problem when additives for imparting various properties other than the essential components (A), (B) and (C) are added.

The present invention will be explained in more detail by the following examples.

Example 1

10 g compound (10% by weight in polyamic acid) having 5 siloxane bonds (n = 5) represented by the following formula as silicone diamine, 57 g of 3,3 ', 4,4'-benzophenone tetracarboxylic acid The dianhydride and 33 g of 4,4'-diaminodiphenyl ether are reacted in N-methylpyrrolidone.

The resulting polyamic acid had a number average molecular weight of 22,000 as measured by GPC, thereby obtaining a high molecular weight polyamic acid with a change in quality.

To the resulting polyamic acid solution (100 parts by weight in terms of solids content) 60 g (60 parts by weight) of methacrylamide and 10 g (10 parts by weight) of mikkel ketones are added and they are dissolved at room temperature.

The resulting solution is coated on an aluminum sheet with a spinner and a film is dried in an oven at 80 ° C. for 1 hour.

The photographic step tablet No. 2 (21 steps) (manufactured by Kodak Co.) was superimposed on this film (in this gray scale, the amount of light transmitted as one step increased at various steps was 1 / √2 of the previous step). And the sensitivity increases as the number of steps remaining in the pattern after development increases), followed by irradiation of 1000 mj / cm 2 UV light with 60% by weight of N-methylpyrrolidone and 40% by weight of methanol. Develop with a composed developing solution and rinse with isopropyl alcohol. Since the pattern of 6 steps or less remains, it turns out that the sensitivity of a film is high.

Separately, a pattern is formed by using a resolution measuring mask (Toppan Printing Co., Ltd., Toppan Test Chart No. 1) as described above. The pattern is decomposed up to 4 μm, which shows high resolution.

Separately, the obtained solution is coated on a silicon wafer, the entire surface is exposed, developed and rinsed, and then thermally cured at 150 ° C, 250 ° C and 350 ° C for 30 minutes in nitrogen.

For the adhesion test, the cured films were cut crosswise to make 100 squares of 1 mm 2 and these squares were peeled off using cellopape (Cellotape, cellophane adhesive tape), but none were peeled off. This indicates a high adhesion. Separately, the obtained solution is coated on an aluminum sheet and the whole is exposed, developed, rinsed and thermoset, and then the aluminum sheet is removed by etching to obtain a film.

The film measured according to JIS K-6760 has a low tensile rate of 210 kg / mm 2.

Therefore, excellent effects (when used for semiconductor parts) of high sensitivity, high resolution, high adhesion and low tensile rate are simultaneously obtained.

Example 2

10 g of a compound (10 wt% in polyamic acid) having one siloxane bond (n = 1) as the silicone diamine, 60 g of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride Water and 30 g of 4,4'-diamino diphenylether are reacted in N-methylferrrolidone.

Thereafter, the same method as in Example 1 is performed. The results were as follows: the number of steps on the step tablet was 8, the resolution was 8 μm, and no square was peeled off in the Cellopape Peeling test. Thus, excellent effects of high sensitivity, high resolution, and high adhesion useful when used for semiconductor parts are obtained simultaneously.

Example 3

A photosensitive resin was obtained in the same manner as in Example 1, except that pyromellitic dianhydride was used instead of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride. Evaluation in the same manner as in 1 gives the following results.

The number of steps of the step tablet was 6, the resolution was 4 µm, no square was peeled off in the cello tape peeling experiment, and the tensile ratio was 210 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 4

After adding 80 parts by weight of N-methylolacrylamide and 5 parts by weight of miklo ketone of 100 parts by weight of the polyamic acid solution (solid content of polyamic acid) obtained in Example 1, stirred at room temperature for 3 hours. To dissolve them and proceed with the reaction.

The resulting solution is coated on aluminum sheet by spinner and dried in an oven at 70 ° C. for 1 hour to obtain a film.

The results of the evaluation are as follows.

The number of steps of the step tablet was 9, the resolution was 3 mu m, and no square was peeled off in the cello tape peeling experiment, and the tensile rate was 230 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 5

A photosensitive resin composition was obtained in the same manner as in Example 4, except that N-methoxymethylacrylamide was used instead of N-methylolacrylamide, and the same evaluation was performed as in Example 4 to obtain the following results. It was.

The number of steps of the step tablet was 9, the resolution was 3 mu m, no square was peeled off in the cellopape peeling experiment, and the tensile rate was 235 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 6

The same procedure as in Example 4 was repeated except that 50 parts by weight of dimethacrylamide having the following formula was used instead of N-methylolacrylamide, and the same evaluation as in Example 4 was performed.

The number of steps of the step tablet was 8, the resolution was 3 mu m, and no square was peeled off in the cello tape peeling experiment, and the tensile rate was 240 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 7

To 100 parts by weight of the polyamic acid solution obtained in Example 1 (solid content of the polyamic acid), 120 parts by weight of an ether type condensate of N-methylolacrylamide and ethylene glycol and 5 parts by weight of a ketone of Micler After the addition, the mixture was stirred at room temperature for 3 hours, and then dissolved and reacted. The results of the evaluation are as follows.

The number of steps of the step tablet was 8, the resolution was 4 µm, no square was peeled off in the cello tape peeling experiment, and the tensile rate was 225 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 8

A photosensitive resin composition was obtained in the same manner as in Example 7, except that an ether type condensate of N-methylol acrylamide and polyvinyl alcohol was used instead of the ether type condensate of N-methylol acrylamide and ethylene glycol. do. Evaluation was carried out in the same manner as in Example 1 to obtain the following results.

The number of steps of the step tablet was 7, the resolution was 3 mu m, no square was peeled off in the cellopape peeling experiment, and the tensile rate was 245 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 9

A polyamic acid solution was prepared in the same manner as in Example 1, except that N, N-dimethylacrylamide was used instead of N-methylpyrrolidone.

To the resulting 612 parts by weight polyamic acid solution (100 parts by weight in terms of solids content) 5 parts by weight of Mikler's ketone (λ max: 365 nm) was added and dissolved at room temperature. The resulting composition is coated on a silicon wafer by a spinner and dried in an oven at 60 ° C. for 1 hour to obtain a film. This film was evaluated in the same manner as in Example 1 to obtain the following results.

The number of steps of the step tablet was 9, the resolution was 3 mu m, and no square was peeled off in the cello tape peeling experiment, and the tensile rate was 210 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 10

The same procedure as in Example 9 was repeated except that N-acryltoyl morpholine was used instead of N, N-dimethylacrylamide, and the same evaluation as in Example 9 was carried out to obtain the following results.

The number of steps of the step tablet was 7, the resolution was 4 µm, no square was peeled off in the cello tape peeling experiment, and the tensile rate was 205 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 11

The polyamic acid obtained in Example 1 was added dropwise to 100 liters of methyl alcohol under vigorous stirring to form a precipitate, and then the precipitate was filtered off. To 100 g of the resulting polyamic acid solution of 100 g of the resulting solid reaction product dissolved in 525 g of N, N-dimethylacrylamide is added 5 g of Mikler's ketone (λmax: 365 nm) and the Mikler's ketone is dissolved at room temperature. Evaluation similar to the above was carried out to obtain the following results.

The number of steps of the step tablet was 9, the resolution was 3 mu m, and no square was peeled off in the cellopape peeling experiment, and the tensile rate was 200 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 12

54 g (0.1 mole) of a compound having five siloxane bonds (n = 5), 322 g (1.0 mole) of 3,3 ', 4,4'-benzophenonetetracarboxylic acid as a silicone diamine, represented by the following formula: The dianhydride and 11.4 g (0.05 mol) of glycerol dimethacrylate are introduced into 2890 g of N-methyl-2-pyrrolidone and their reaction proceeds at 50 ° C. for 16 hours.

Then, 180 g (0.9 mole) of 4,4'-diaminodiphenyl ether was introduced thereto, and their reaction was carried out at 20 ° C. for 6 hours.

To the resulting 612 parts by weight of polyamic acid solution (100 parts by weight in terms of solids content) 50 parts by weight of methacrylamide and 5 parts by weight of myckler ketone (λ max: 365 nm) were added and dissolved at room temperature.

Subsequently, the same evaluation as in Example 1 was carried out to obtain the following results.

The number of steps of the step tablet was 7, the resolution was 3 mu m, and no square was peeled off in the cello tape peeling experiment, and the tensile rate was 240 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 13

25 g (0.1 mole) of a compound having one siloxane bond (n = 1), 322 g (1.0 mole) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 11.4 g ( 0.05 mole) of glycerol dimethacrylate is introduced into 2890 g of N, N-dimethylacrylamide and their reaction proceeds at 50 ° C. for 16 hours.

Then, 180 g (0.9 mole) of 4,4'-diaminodiphenyl ether was introduced thereto, and their reaction was carried out at 20 ° C. for 6 hours.

To 612 g (100 g in terms of solids content) of the resulting polyamic acid solution is added 50 g of Mikler ketone (λ max: 365 nm) and dissolved at room temperature. The resulting composition is coated on a silicon wafer with a spinner and dried in an oven at 50 ° C. for 1 hour to obtain a film. The film was evaluated in the same manner as in Example 9 to obtain the following results.

The number of steps of the step tablet was 12, the resolution was 3 µm, and no square was peeled off in the cello tape peeling experiment. Thus, excellent effects of high sensitivity, high resolution, and high adhesion useful when used in semiconductor parts are obtained simultaneously.

Example 14

A photosensitive resin composition was obtained in the same manner as in Example 13 except for using 2-hydroxyethyl methacrylate instead of glycerol dimethacrylate. The composition was evaluated as in Example 13 to obtain the following results.

The number of steps of the step tablet was 11, the resolution was 3 µm, and no square was peeled off in the cello tape peeling experiment. Thus, excellent effects of high sensitivity, high resolution, and high adhesion useful when used in semiconductor parts are obtained simultaneously.

Example 15

As in Example 13, except that 4 g (4 parts by weight) of 2- (p-dimethylaminostyryl) benzoxazole and 8 g (8 parts by weight) of N-phenylglycine were used in place of Mikler's ketone. The photosensitive resin composition was obtained by the method, and the same evaluation as in Example 13 was carried out to obtain the following results.

The number of steps of the step tablet was 10, the resolution was 3 mu m, no square was peeled off in the cellopape peeling experiment, and the tensile rate was 205 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 16

A photosensitive resin composition was obtained in the same manner as in Example 13, except that 4 g of 2- (p-dimethylaminostyryl) benzoxazole and 8 g of phenyloxazolone were used instead of the Mikler ketone. The evaluation as described above was carried out to obtain the following results.

The number of steps of the step tablet was 9, the resolution was 3 mu m, and no square was peeled off in the cello tape peeling experiment, and the tensile rate was 210 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 17

A photosensitive resin composition was obtained in the same manner as in Example 13, except that 4 g of 3,3'-carbonyl-bis (7-dimethylaminocoumarin) and 8 g of N-phenylglycine were used in place of Mikler's ketone. And the same evaluation as in Example 13 was carried out to obtain the following results.

The number of steps of the step tablet was 10, the resolution was 4 µm, no square was peeled off in the cello tape peeling experiment, and the tensile ratio was 215 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 18

A photosensitive resin composition was prepared in the same manner as in Example 13, except that 4 g of 3,3'-carbonyl-bis (7-dimethylaminocoumarin) and 8 g of N-phenyloxazolone were used in place of the Mikler ketone. Then, the same evaluation as in Example 13 was carried out to obtain the following results.

The number of steps of the step tablet was 8, the resolution was 4 µm, no square was peeled off in the cello tape peeling experiment, and the tensile rate was 230 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 19

4 g (4 parts by weight) of 2- (p-dimethylaminostyryl) benzoxazole and 8 g (8 parts by weight) of N-phenylglycine in place of Micler's ketone and 12 g (12 parts by weight) of N, A photosensitive resin composition was obtained in the same manner as in Example 13 except that N-dimethylaminoethyl methacrylate was further added. The same evaluation as in Example 13 was carried out to obtain the following results.

The number of steps of the step tablet was 13, the resolution was 3 mu m, no square was peeled off in the cello tape peeling experiment, and the tensile rate was 235 kg / mm 2. Thus, excellent effects of high sensitivity, high resolution, high adhesion, and low tensile rate, which are useful when used in semiconductor parts, are simultaneously obtained.

Example 20

The photosensitive resin composition obtained in Example 1 was spin-coated by a spinner on a silicon wafer on which an ultra-LSI (1M bit) semiconductor component circuit was to be made, and dried in an oven at 80 ° C. for 1 hour to apply to the entire surface of the wafer. A polyamide film is formed.

Thereafter, the film is exposed and developed and the film of the bond pad portion is removed. Subsequently, the wafers were heat-treated at 150 ° C., 250 ° C. and 350 ° C. for 30 minutes, and the wafers were lined to cut into 6 × 12 mm square chips. The semiconductor component is mounted on a metal frame and bonded with a gold wire, and then sealed with an epoxy molding compound. The resulting semiconductor device had no breakage for more than 2000 hours in the high temperature, high humidity, and high bias test (using 85 ° C., 85% RH and 10 V) and the pressure cooker test (125 ° C., 2.3 atm), and also α No errors were found by the line.

Similarly, excellent semiconductor devices were obtained in the same manner as above using the compositions obtained in Examples 2, 3, 4, 9, 12 and 13.

Example 21

The photosensitive resin composition obtained in Example 1 was used to make a semiconductor device having a two-layer wiring structure.

After coating the photosensitive resin composition on the silicon wafer on which the semiconductor component circuit is to be made, the coated film is exposed, developed, and cured to form a 1.5 μm thick polyamide insulator with through-holes. Form. Subsequently, aluminum wiring is formed as a second layer by sputtering and connected to an under circuit. In addition, a polyamide insulator is formed using the photosensitive resin composition in the same manner as the first layer. Further, a silicon nitride film is formed by a plasma CVD apparatus, and a film using the above photosensitive resin having a thickness of 4 µm is further formed thereon. The silicon nitride film is etched using a polyamide film as a resist to make an electrode. Lines are drawn on the silicon wafer and cut into 5 x 6 mm square chips. The semiconductor part is mounted on a metal frame, bonded with a gold wire, and sealed with an epoxy molding compound. The resulting semiconductor device did not show any breakage for more than 2000 hours in the high temperature, high humidity and high bias test (using 85 ° C., 85% RH, 10 V) and the pressure cooker test (125 ° C., 2.3 atmospheres). In addition, no error operation was caused due to the α-ray.

In addition, excellent semiconductor devices are obtained in the same manner as above using the compositions obtained in Examples 2, 3, 4, 9, 12 and 13.

Example 22

A copper wiring was formed by electroless plating or electroplating on a 50 mm square alumina ceramic substrate on which the polyamide film was to be made, and the photosensitive resin composition obtained in Example 13 was coated, exposed, developed and cured to An amide insulating layer is formed. In addition, copper wiring is formed as a second layer by non-plating or electroplating. This method is repeated to make a four-layer wiring board. It was found that the substrate had almost no change in connection resistance even after 2000 thermal shock cycle tests at -65 ° C to 125 ° C, and the substrate was excellent. Two LSIs are connected using these substrates. This high density assembly substrate has a 30% improvement in wiring delay time compared to conventional ceramic wiring boards.

Comparative Example 1

Except for using methyl methacrylate instead of methacrylamide, a resin composition is obtained by the same method as Example 1, and the composition is evaluated similarly to Example 1. Since the photosensitizer is inferior in compatibility with polyamic acid because there is no amide group, a pattern cannot be formed.

Comparative Example 2

A photosensitive resin composition was obtained in the same manner as in Example 1 except that diethylene glycol dimethacrylate was used instead of methacrylamide, and the same evaluation was performed. Since the photosensitizer is inferior in compatibility with polyamic acid because there is no amide group, a pattern cannot be formed.

Comparative Example 3

The compounding is carried out in the same manner as in Example 9 except that N-methyl-2-pyrrolidone is used instead of N, N-dimethylacrylamide. The composition does not exhibit a reaction to light. Therefore, 60 parts by weight of dimethylaminoethyl methacrylate is further added as a compound having an amino group and a carbon-carbon double bond capable of dimerizing or polymerizing by actinic radiation. The coating of the composition and the evaluation of the coated film are carried out in the same manner as in Example 9. The step tablet has only five steps, which means its sensitivity is low. In addition, when the viscosity change of the composition was measured at room temperature (23 ° C), the viscosity decreased by 20% after 3 days.

[Comparative Example 4]

The photosensitive resin composition was obtained by the method similar to Example 1 except not using a Mikler ketone, and the same evaluation as Example 1 is performed. The photo-reaction does not proceed effectively, and during development, the pattern completely flows out, which in fact cannot be used.

[Comparative Example 5]

After dissolving 290 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 244 g of 2-hydroxyethyl methacrylate in γ-butyrolactone, 150 g of pyridine was used as a catalyst. The reaction was carried out at 20 ° C. for 24 hours to obtain an esterified product. Subsequently, dicyclohexylcarbodiamide was added as an amide formation reaction catalyst, followed by 180 g of 4,4'-diaminophenyl ether and 55 g of five siloxane bonds (n = 5) represented by the following formula as silicone diamine. Further compounds are added and their reaction proceeds at 20 ° C. for 8 hours.

The resulting slurry is then filtered and the filtrate is added dropwise to 350 liters of ethanol under vigorous stirring to precipitate the polymer, which is allowed to stand for 12 hours. The precipitate is filtered, dried and milled. The resulting polymer has a molecular weight of 2000, which is significantly smaller than expected. Thus, another polymer was made again in the same manner, but even in this case, the molecular weight was only 3300. Not only does this method require a long time in complex steps, but the product also exhibits several changes in quality.

This polymer is then dissolved in N-methyl-2-pyrrolidone and a photosensitizer as used in Example 1 is added to the solution to obtain a photosensitive resin composition. The composition was evaluated in the same manner as in Example 1 to obtain the following results. The number of steps of the step tablet was 3, the resolution was 10 占 퐉, the pattern was messed up in shape, and all squares were removed in the cello tape peeling experiment. Thus, it was found that the composition could not be used in practice.

Claims (23)

As an essential ingredient, (A) an acid anhydride-terminated polyamic acid, the polyamic acid represented by the following general formula (III) in which both ends thereof are substituted with actinic reactor P *, [In the formula, 0.5 to 50 mol% of R ₁ is composed of a silicone diamine residue represented by the following formula (II), Wherein n represents an integer of 1 to 50. The remaining 50 to 99.5 mol% of R ₁ is composed of an organic group selected from the group consisting of an aromatic group, an aliphatic group, an aliphatic ring group and a heterocyclic group, and R ₂ is aromatic And an organic group selected from the group consisting of a group, an aliphatic group, an aliphatic ring group, a heterocyclic group and a silicon group, m 'represents an integer of 10 to 10000, and P ^* is represented by the following formula: (Wherein R ₃ is H or CH ₃ , R ₄ represents an organic residue and n ′ is an integer from 1 to 5) (B) an amide compound having a carbon-carbon double bond, and The photosensitive resin composition containing (C) 10-500 weight part of (B) amide compounds and 0.1-50 weight part of (C) photosensitizers with respect to 100 weight part of (A) polyamic acids. The photosensitive resin composition of Claim 1 whose sock short term P ^* of polyamic acid (A) is 2-hydroxyethyl methacrylate or an acrylate residue represented by following formula (IV). (Wherein R ₃ represents H or CH ₃ ) The photosensitive resin composition of Claim 1 whose short term P * is a glycerol dimethacrylate or diacrylate residue represented by following formula (V). (Wherein R ₃ represents H or CH ₃ ) The silicone diamine residue according to claim 1, 2 or 3, which is a comonomer of the polyamic acid (A), is the formula (VI), which corresponds to formula (2) wherein n is 1 The photosensitive resin composition represented by. 4. The silicone diamine residue according to claim 1, 2 or 3, which is a comonomer of polyamic acid (A), is represented by the formula (VII), which corresponds to formula (2) wherein n is 5 to 20: The photosensitive resin composition shown. (Wherein n is 5 to 20) The polyamic acid (A) according to claim 1, 2 or 3, wherein the polyamic acid (A) is a main component of silicone diamine, 4,4'-diaminodiphenyl ether and pyromellitic dianhydride or 3,3 ', 4, Photosensitive resin composition manufactured from 4'- benzophenone tetracarboxylic dianhydride. The photosensitive resin composition of Claim 1, 2 or 3 whose amide compound (B) which has a carbon-carbon double bond is a liquid at room temperature. The photosensitive resin composition according to claim 1, 2 or 3, wherein the polyamic acid (A) is a liquid at room temperature and is obtained by reacting a carbon-carbon double bond in an amide compound. The photosensitive resin composition of Claim 1, 2 or 3 whose amide compound (B) which has a carbon-carbon double bond is acrylamide or methacrylamide. The photosensitive resin of Claim 1, 2 or 3 whose amide compound (B) which has a carbon-carbon double bond is a dialkylacrylamide compound or a dialkyl methacrylamide compound represented by following formula (VIII). Composition. (Wherein R ₅ and R ₆ each represent CH ₃ or C ₂ H ₅ , and R ₇ represents H or CH ₃ ) The photosensitive resin composition of Claim 1, 2 or 3 whose amide compound (B) which has a carbon-carbon double bond is N-acryloyl morpholine. The N-methylol acrylamide or methacrylamide derivative or N-alkoxy of claim 1, 2 or 3, wherein the amide compound (B) having a carbon-carbon double bond is represented by the following formula (IX): Photosensitive resin composition which is a methylacrylamide or methacrylamide derivative. Wherein R ₈ represents H, CH ₃ , C ₂ H ₅ , CH ₂ OH, or CH ₂ OCH ₃ , and R ₉ represents —CH ₂ OH, —CH ₂ OCH ₃ , —CH ₂ OC ₂ H ₂ , -CH ₂ OC ₃ H ₇ or -CH ₂ OC ₄ H ₉ , R ₁₀ represents H or CH ₃ ) The photosensitive resin composition of Claim 1, 2 or 3 whose amide compound (B) which has a carbon-carbon double bond is a diacrylamide or a dimethacrylamide compound represented by following formula (X). Wherein R ₁₁ represents H or CH ₃ The photosensitive resin composition of Claim 1, 2 or 3 whose amide compound (B) which has a carbon-carbon double bond is an ether type condensate of N-methylol acrylamide or methacrylamide and a polyhydric alcohol. The photosensitive resin composition of Claim 1, 2 or 3 whose absorption maximum wavelength (lambda) max of a photosensitizer (C) is 330-500 nm. The photosensitive resin composition of Claim 1, 2 or 3 whose photosensitizer (C) is a styryl compound represented by following General formula (XI). [Wherein, R ₁₂ represents -H, -CH ₃ , -C ₂ H ₅ or -C ₆ H ₅ , R ₁₃ is (Wherein R represents H, CH ₃ or C ₂ H ₅ ). The photosensitive resin composition of Claim 1, 2 or 3 whose photosensitizer (C) is a glycine compound represented by following General formula (XII). (Wherein, R ₁₄ is _{-H, -CH 3, -C 2 H} 5, -C 6 H 5, -OCH 3, -OCOCH 3, -OC 2 H 5, -OCO 2 H 5, N (CH 3 ), 2, -N (C ₂ H ₅ ) ₂ , -NHCOOCH ₃ , -COCH ₃ , -COC ₂ H ₅ , -NHCONH ₂ , -CH ₂ OH, -OH, -CH (CH ₃ ) ₂ or -C (CH ₃ ) _3. ) The photosensitive resin composition of Claim 1, 2 or 3 whose photosensitizer (C) is a biscumarin compound substituted with the carbonyl group in the 3-position represented by following General formula (XIII). Wherein R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkoxy group or a dialkylamino group.) The photosensitive resin composition of Claim 1, 2 or 3 whose photosensitizer (C) is an oxazolone compound represented with a following general formula (XIV). Wherein R ₁₇ is or Indicates, R ₁₈ represents —H, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₆ H ₅ , —OH, —OCH ₃ or —OC ₂ H ₅ ) The photosensitive resin composition of Claim 1, 2 or 3 in which a photosensitizer (C) further contains the dialkylaminoacrylate or methacrylate compound represented by following General formula (XV). (Wherein R ₁₉ and R ₂₀ each represent CH ₃ or C ₂ H ₅ , R ₂₁ represents H or CH ₃ and p is 2 or 3) 21. A photosensitive resin composition according to any one of claims 1 and 2 to 20 is coated on a surface of a semiconductor component, the composition is exposed and developed to form a pattern, and then the pattern is heat-cured to form the surface of the semiconductor component. The semiconductor device attached to the. The photosensitive resin composition according to any one of claims 1 and 2 to 20 is coated on the surface of a semiconductor component, the composition is exposed and developed to form a pattern, the pattern is heat-cured, and the conductor circuit is wired. And repeating a wiring procedure consisting of connecting a circuit to a lower conductor layer. A pattern is formed on a substrate of silicon or alumina using the photosensitive resin composition according to any one of claims 1 and 2 to 20 to form an insulating layer, and then the conductor circuit is wired, and the circuit is connected to the lower conductor layer. And a wiring procedure characterized by connecting the obtained product with the semiconductor component.